Bridging the two cultures. Commercial archaeology and the study of prehistoric Britain

This paper was given at a meeting of the Society held on 12 January 2006 and it discusses the relationship between academic research and developer-funded archaeology in Britain today, highlighting the strengths and weaknesses of each. It considers the relationship between archaeological theory and practice and discusses the changing roles of academics, fieldworkers and managers. It argues that important issues need to be resolved, including the dissemination of information from recent archaeological fieldwork and the use of ‘grey literature’ in informing more ambitious interpretations of the past.

Stereo and motion parallax cues in human 3D vision: can they vanish without a trace?

In an immersive virtual reality environment, subjects fail to notice when a scene expands or contracts around them, despite correct and consistent information from binocular stereopsis and motion parallax, resulting in gross failures of size constancy (A. Glennerster, L. Tcheang, S. J. Gilson, A. W. Fitzgibbon, & A. J. Parker, 2006). We determined whether the integration of stereopsis/motion parallax cues with texture-based cues could be modified through feedback. Subjects compared the size of two objects, each visible when the room was of a different size. As the subject walked, the room expanded or contracted, although subjects failed to notice any change. Subjects were given feedback about the accuracy of their size judgments, where the “correct” size setting was defined either by texture-based cues or (in a separate experiment) by stereo/motion parallax cues. Because of feedback, observers were able to adjust responses such that fewer errors were made. For texture-based feedback, the pattern of responses was consistent with observers weighting texture cues more heavily. However, for stereo/motion parallax feedback, performance in many conditions became worse such that, paradoxically, biases moved away from the point reinforced by the feedback. This can be explained by assuming that subjects remap the relationship between stereo/motion parallax cues and perceived size or that they develop strategies to change their criterion for a size match on different trials. In either case, subjects appear not to have direct access to stereo/motion parallax cues.

The relationships of time and temperature to body weight and numbers of endospores in Pasteuria penetrans-infected Meloidogyne javanica females

Tomato plants inoculated with Meloidogyne javanica juveniles infected with Pasteuria penetrans were grown in a glasshouse (20-32degreesC) for 36, 53, 71 and 88 days and in a growth room (26-29degreesC) for 36, 53, 71 and 80 days. Over these periods the numbers of P penetrans endospores in infected M. javanica females and the weights of individual infected females increased. In the growth room, most spores (2.03 x 10(6)) were found after 71 days. However, in the glasshouse the rate of increase was slower and spore numbers were still increasing at the final sampling at 88 days (2.04 x 10(6)), as was the weight of the nematodes (72 mug). Weights of uninfected females reached a maximum of 36.2 and 43.1 mug after 71 days in the growth room and glasshouse, respectively.

A surface and catalytic study of heterogenised Os-3(CO)(12) species in MCM-41 structures

Immobilised Os species prepared via chemical vapour deposition (CVD) of Os-3(CO)(12) onto MCM-41 are active and selective catalysts for the dihydroxylation of trans-stilbene in acetone and water, using N-methylmorpholine N-oxide as the oxidant. A detailed temperature programmed decomposition study of the solids enables to identify the active sites as Os-x(CO)(y) surface species. The initial loading of the MCM-41 with the trinuclear precursor, as well as the temperature of the post-synthesis oxidising treatment, are found to have a significant impact on the structure/geometry of the resulting surface species, and thus their catalytic properties. We show how it is also affected by the confined environment of the MCM-41 mesopores and especially the curvature of the 30 Angstrom diameter channels. Finally, a careful study of the catalytic properties of the materials together with a study of the reactivity of the reaction products under similar conditions enable to suggest a mechanism involving the reaction of the oxidant with the osmium carbonyl surface species to form the catalytically active Os-oxo sites, and the formation of an osmoate-type species (through adsorption of the alkene onto the Os-oxo site) which subsequently reacts with the solvent to produce the diol. (C) 2003 Elsevier B.V. All rights reserved.

A rheological and SAXS study of the lamellar order in a side-on liquid crystalline block copolymer

We study the structure and shear flow behavior of a side-on liquid crystalline triblock copolymer, named PBA-b-PA444-b-PBA (PBA is poly(butyl acrylate) and PA444 is a poly(acrylate) with a nematic liquid crystal side-on mesogen), in the self-assembled lamellar phase and in the disordered phase. Simultaneous oscillatory shear and small-angle X-ray scattering experiments show that shearing PBA-b-PA444-b-PBA at high frequency and strain amplitudes leads to the alignment of the lamellae with normals perpendicular to the shear direction and to the velocity gradient direction, i.e., in the perpendicular orientation. The order-to-disorder transition temperature (T-ODT) is independent of the applied strain, in contrast to results reported in the literature for coil-coil diblock copolymers, which show an increase in T-ODT with shear rate. It is possible that in our system, T-ODT does not depend on the applied strain because the fluctuations are weaker than those present in coil-coil diblock copolymer systems.

The synthesis of novel 3-substituted polypyrroles bearing crown-ether moieties and a study of their electrochemical properties

A series of fourteen novel pyrrole monomers substituted at the 3-position with aliphatic and aromatic crown-ether moieties have been synthesised in good yield and characterised extensively. Several of these compounds were electropolymerised successfully in acetonitrile, using both potentiostatic and galvanostatic modes and the electrochemical properties of those systems were studied via cyclic voltammetry in aqueous and organic media. Novel crown-ether substituted polypyrrole derivatives revealed reversible redox couples in LiClO4/CH3CN (0.1 M). The morphology of these novel crown-ether substituted polypyrrole derivatives was characterised by scanning electron microscopy. These polymers exhibited an open porous structure and half the charge was required when compared to polypyrrole to afford films of equal thickness. The mass change during polymerisation was followed by electrochemical quartz crystal microbalance measurement, and the rate of polymer growth was found to be nonlinear when compared to polypyrrole. (c) 2005 Elsevier B.V. All rights reserved.

Design and theoretical study of nickel catalysts for syndiotactic polyolefins

A nickel catalyst was modeled with ligand L-2, [ NH = CH-CH = CH-O](-), which should have potential use as a syndiotactic polyolefin catalyst, and the reaction mechanism was studied by theoretical calculations using the density functional method at the B3LYP/ LANL2MB level. The mechanism involves the formation of the intermediate [(NiLMe)-Me-2](+), in which the metal occuples a T-shaped geometry. - This intermediate has two possible structures with the methyl group trans either to the oxygen or to the nitrogen atom of L-2. The results show that both structures can lead to the desired product via similar reaction paths, A and B. Thus, the polymerization could be considered as taking place either with the alkyl group occupying the position trans to the Ni-O or trans to the Ni-N bond in the catalyst. The polymerization process thus favors the catalysis of syndiotactic polyolefins. The syndiotactic synthesis effects could also be enhanced by variations in the ligand substituents. From energy considerations, we can conclude that it is more favorable for the methyl group to occupy the trans-O position to form a complex than to occupy the trans-N position. From bond length considerations, it is also more favoured for ethene to occupy the trans-O position than to occupy the trans-N position.

Incorporation of a sodium ion guest in the host of copper(II)-Schiff-base complexes: Structural characterization and magnetic study

Three copper(II) complexes, [CuL1], [CuL2] and [CuL3] where L-1, L-2 and L-3 are the tetradentate di-Schiff-base ligands prepared by the condensation of acetylacetone and appropriate diamines (e.g. 1,2-diaminoethane, 1,2-diaminopropane and 1,3-diaminopropane, respectively) in 2:1 ratios, have been prepared. These complexes act as host molecules and include a guest sodium ion by coordinating through the oxygen atoms to result in corresponding new trinuclear complexes, [(CuL1)(2)Na(ClO4)(H2O)][CuL1], [(CuL2)(2)Na(ClO4)(H2O)] (2) and [(CuL3)(2)Na(ClO4)(H2O)] (3) when crystallized from methanol solution containing sodium perchlorate. All three complexes have been characterized by single crystal X-ray crystallography. In all the complexes, the sodium cation has a six-coordinate distorted octahedral environment being bonded to four oxygen atoms from two Schiff-base complexes of Cu(II) in addition to a perchlorate anion and a water molecule. The copper atoms are four coordinate in a square planar environment being bonded to two oxygen atoms and two nitrogen atoms of the Schiff-base ligand. The variable temperature susceptibilities for complexes 1-3 were measured over the range 2-300 K. The isotropic Hamiltonian, H = g(1)beta HS1 + g(2)beta HS2 + J(12)S(1)S(2) + g(3)beta HS3 for complex 1 and H = g(1)beta HS1 + g2 beta HS2 +J(12)S(1)S(2) for complexes 2 and 3 has been used to interpret the magnetic data. The best fit parameters obtained are: g(1) = g(2) = 2.07(0), J = - 1.09(1) cm(-1) for complex 1, g(1) = g(2) = 2.06(0), J = -0.55(1) cm(-1) for complex 2 and g1 = g2 = 2.07(0).J = -0.80(1) cm(-1) for 3. Electrochemical studies displayed an irreversible Cu(II)/Cu(I) one-electron reduction process. (C) 2008 Elsevier Ltd. All rights reserved.

Experimental and theoretical study of the infrared spectra of BrHI- and BrDI-

Gas phase vibrational spectra of BrHI- and BrDI- have been measured from 6 to 17 mum (590-1666 cm-1) using tunable infrared radiation from the free electron laser for infrared experiments in order to characterize the strong hydrogen bond in these species. BrHI-.Ar and BrDI-.Ar complexes were produced and mass selected, and the depletion of their signal due to vibrational predissociation was monitored as a function of photon energy. Additionally, BrHI- and BrDI- were dissociated into HBr (DBr) and I- via resonant infrared multiphoton dissociation. The spectra show numerous transitions, which had not been observed by previous matrix studies. New ab initio calculations of the potential-energy surface and the dipole moment are presented and are used in variational ro-vibrational calculations to assign the spectral features. These calculations highlight the importance of basis set in the simulation of heavy atoms such as iodine. Further, they demonstrate extensive mode mixing between the bend and the H-atom stretch modes in BrHI- and BrDI- due to Fermi resonances. These interactions result in major deviations from simple harmonic estimates of the vibrational energies. As a result of this new analysis, previous matrix-isolation spectra assignments are reevaluated. (C) 2004 American Institute of Physics.

Solid phases of cyclopentane: combined experimental and simulation study

The phase diagram of cyclopentane has been studied by powder neutron diffraction, providing diffraction patterns for phases I, II, and III, over a range of temperatures and pressures. The putative phase IV was not observed. The structure of the ordered phase III has been solved by single-crystal diffraction. Computational modeling reveals that there are many equienergetic ordered structures for cyclopentane within a small energy range. Molecular dynamics simulations reproduce the structures and diffraction patterns for phases I and III and also show an intermediate disordered phase, which is used to interpret phase II.

Deprotection, tethering, and activation of a one-legged metalloporphyrin on a chemically active metal surface: NEXAFS, Synchrotron XPS, and STM study of [SAc]P-Mn(III)Cl on Ag(100)

The structural and reactive properties of the acetyl-protected "one-legged" manganese porphyrin [SAc]P-Mn(III)Cl on Ag(100) have been studied by NEXAFS, synchrotron XPS and STM Spontaneous surface-mediated deprotection occurs at 300 K accompanied by spreading of the resulting thio-tethered porphyrin across the metal surface Loss of the axial chlorine ligand occurs at 498 K, without any demetalation of the macrocycle, leaving the Mn center in a low co-ordination state At low coverages the macrocycle is markedly tilted toward the silver surface, as is the phenyl group that forms part of the tethering "leg". In the monolayer region a striking transition occurs whereby the molecule rolls over, preserving the tilt angle of the phenyl group, strongly increasing that of the macrocycle, decreasing the apparent height of the molecule and decreasing its footprint, thus enabling closer packing These findings are in marked contrast with those previously reported for the corresponding more rigidly bound four-legged porphyrin [Turner, M., Vaughan, O. P. H., Kyriakou, G., Watson, D. J., Scherer, L. J; Davidson, G J. E, Sanders, J. K. M.; Lambert, R. M J. Am. Chem Soc 2009, 131, 1910] suggesting that the physicochemical :)properties and potential applications of these versatile systems should be strongly dependent on the mode of tethering to the surface.

C-H...O hydrogen bonding in 4-phenyl-benzaldehyde: a comprehensive crystallographic, spectroscopic and computational study

The crystal structure of 4-phenyl-benzaldehyde reveals the presence of a dimer linked by the C=O and C( 9)-H groups of adjacent molecules. In the liquid phase, the presence of C-(HO)-O-... bonded forms is revealed by both vibrational and NMR spectroscopy. A Delta H value of - 8.2 +/- 0.5 kJ mol(-1) for the dimerisation equilibrium is established from the temperature-dependent intensities of the bands assigned to the carbonyl-stretching modes. The NMR data suggest the preferential engagement of the C(2,6)-H and C(10/12)/C(11)-H groups as hydrogen bond donors, instead of the C(9)-H group. While ab initio calculations for the isolated dimers are unable to corroborate these NMR results, the radial distribution functions obtained from molecular dynamics simulations show a preference for C(2,6)-H and C(10/12)/C(11)-(HO)-O-... contacts relative to the C(9)-(HO)-O-... ones.

Microglial activation correlates with severity in Huntington disease: a clinical and PET study

Background: Huntington disease ( HD) is characterized by the progressive death of medium spiny dopamine receptor bearing striatal GABAergic neurons. In addition, microglial activation in the areas of neuronal loss has recently been described in postmortem studies. Activated microglia are known to release neurotoxic cytokines, and these may contribute to the pathologic process. Methods: To evaluate in vivo the involvement of microglia activation in HD, the authors studied patients at different stages of the disease using [ C-11]( R)-PK11195 PET, a marker of microglia activation, and [ C-11] raclopride PET, a marker of dopamine D2 receptor binding and hence striatal GABAergic cell function. Results: In HD patients, a significant increase in striatal [ C-11]( R)-PK11195 binding was observed, which significantly correlated with disease severity as reflected by the striatal reduction in [ C-11] raclopride binding, the Unified Huntington's Disease Rating Scale score, and the patients' CAG index. Also detected were significant increases in microglia activation in cortical regions including prefrontal cortex and anterior cingulate. Conclusions: These [ C-11]( R)-PK11195 PET findings show that the level of microglial activation correlates with Huntington disease ( HD) severity. They lend support to the view that microglia contribute to the ongoing neuronal degeneration in HD and indicate that [ C-11]( R)-PK11195 PET provides a valuable marker when monitoring the efficacy of putative neuroprotecting agents in this relentlessly progressive genetic disorder.